Purified acetylated derivatives of castor oil and compositions including same

ABSTRACT

The present disclosure is directed to a single phase acetylated castor component (SP-ACC). An acetylated castor component is purified to produce the SP-ACC which contains a reduced amount of, or no, insoluble component(s) therein. The SP-ACC enhances the performance and properties of plasticizers of which it is a component.

PRIORITY

This application claims priority to U.S. Patent Application No.61/247,383 filed on Sep. 30, 2009, the entire content of which isincorporated by reference herein.

BACKGROUND

Plasticizers are compounds or mixtures of compounds that are added topolymer resins to impart softness and flexibility. Phthalic aciddiesters (also known as “phthalates”) are known plasticizers in manyflexible polymer products, such as polymer products formed frompolyvinyl chloride (PVC) and other vinyl polymers. Examples of commonphthalate plasticizers include di-isononyl phthalate (DINP), diallylphthalate (DAP), di-2-ethylhexyl-phthalate (DEHP), dioctyl phthalate(DOP) and diisodecyl phthalate (DIDP). Other common plasticizers, usedfor high temperature applications, are trimellitates and adipicpolyesters. Mixtures of plasticizers are often used to obtain optimumproperties.

Phthalate plasticizers have recently come under intense scrutiny bypublic interest groups that are concerned about the negativeenvironmental impact of phthalates and potential adverse health effectsin humans (especially children) exposed to phthalates.

Consequently, a need exists for phthalate-free plasticizers for polymerresins. A need further exists for phthalate-free plasticized polymersthat have the same, or substantially the same, chemical, mechanical,and/or physical properties as polymers containing phthalateplasticizers.

SUMMARY

The present disclosure is directed to an acetylated castor componentwith reduced, or no, insoluble component(s) therein. The acetylatedcastor component is purified to remove insoluble components to produce asingle phase acetylated castor component. The single phase acetylatedcastor component enhances the performance and properties of plasticizersof which it is part.

The present disclosure provides a component. In an embodiment, a singlephase acetylated castor component is provided and contains less thanabout 0.2 wt % insoluble components after exposure to 15° C. for atleast one week.

The present disclosure provides a composition. In an embodiment, acomposition is provided and includes a single phase acetylated castorcomponent and an epoxidized fatty acid ester. The composition containsless than 0.2 wt % insoluble components after exposure to 15° C. for atleast one week.

The present disclosure provides a polymeric composition. In anembodiment, a polymeric composition is provided and includes a polymericresin and a plasticizer composition. The plasticizer compositionincludes a single phase acetylated castor component and optionally anepoxidized fatty acid ester. The polymeric composition has a loop spewvalue from 0-2 as measured in accordance with ASTM D 3291.

The disclosure provides a conductor. In an embodiment, a coatedconductor is provided and includes a metal conductor and a coating onthe metal conductor. The coating includes a polymeric resin and aplasticizer composition. The plasticizer includes a single phaseacetylated castor component and optionally an epoxidized fatty acidester.

An advantage of the present disclosure is a bio-based plasticizer withreduced, or no, loop spew.

An advantage of the present disclosure is a phthalate-free and/orlead-free bio-based based plasticizer.

An advantage of the present disclosure is a bio-based plasticizer thatreduces greenhouse gases.

An advantage of the present disclosure is a bio-based plasticizer whichenables users to obtain LEED credits.

An advantage of the present disclosure is a bio-based plasticizer whichenables users to obtain carbon credits.

An advantage of the present disclosure is a coating for wire and cableapplications that is phthalate-free and lead-free.

An advantage of the present disclosure is a phthalate-free bio-basedplasticizer that produces little, or no, loop spew when applied as awire/cable coating.

DETAILED DESCRIPTION

The present disclosure is directed to single phase acetylated castorcomponents and compositions including the same. The compositionsprovided herein are suitable for use as plasticizers in polymer resinsand in wire and cable jacketing and insulation in particular.

All references to the Periodic Table of the Elements refer to thePeriodic Table of the Elements published and copyrighted by CRC Press,Inc., 2003. Also, any references to a Group or Groups shall be to theGroup or Groups reflected in this Periodic Table of the Elements usingthe IUPAC system for numbering groups. Unless stated to the contrary,implicit from the context, or customary in the art, all parts andpercents are based on weight and all test methods are current as of thefiling date of this disclosure. For purposes of United States patentpractice, the contents of any referenced patent, patent application orpublication are incorporated by reference in their entirety (or itsequivalent U.S. version is so incorporated by reference) especially withrespect to the disclosure of synthetic techniques, product andprocessing designs, polymers, catalysts, definitions (to the extent notinconsistent with any definitions specifically provided in thisdisclosure), and general knowledge in the art.

The numerical ranges in this disclosure are approximate, and thus mayinclude values outside of the range unless otherwise indicated.Numerical ranges include all values from and including the lower and theupper values, in increments of one unit, provided that there is aseparation of at least two units between any lower value and any highervalue. As an example, if a compositional, physical or other property,such as, for example, molecular weight, melt index, etc., is from 100 to1,000, then the intent is that all individual values, such as 100, 101,102, etc., and sub ranges, such as 100 to 144, 155 to 170, 197 to 200,etc., are expressly enumerated. For ranges containing values which areless than one or containing fractional numbers greater than one (e.g.,1.1, 1.5, etc.), one unit is considered to be 0.0001, 0.001, 0.01 or0.1, as appropriate. For ranges containing single digit numbers lessthan ten (e.g., 1 to 5), one unit is typically considered to be 0.1.These are only examples of what is specifically intended, and allpossible combinations of numerical values between the lowest value andthe highest value enumerated, are to be considered to be expresslystated in this disclosure. Numerical ranges are provided within thisdisclosure for, among other things, the amounts for components in thecomposition and/or coating, additives, and various other components inthe composition, and the various characteristics and properties by whichthese components are defined.

As used with respect to a chemical compound, unless specificallyindicated otherwise, the singular includes all isomeric forms and viceversa (for example, “hexane”, includes all isomers of hexaneindividually or collectively). The terms “compound” and “complex” areused interchangeably to refer to organic-, inorganic- and organometalliccompounds. The term, “atom” refers to the smallest constituent of anelement regardless of ionic state, that is, whether or not the samebears a charge or partial charge or is bonded to another atom. The term“amorphous” refers to a polymer lacking a crystalline melting point asdetermined by differential scanning calorimetry (DSC) or equivalenttechnique.

The terms “comprising”, “including”, “having” and their derivatives arenot intended to exclude the presence of any additional component, stepor procedure, whether or not the same is specifically disclosed. Inorder to avoid any doubt, all compositions claimed through use of theterm “comprising” may include any additional additive, adjuvant, orcompound whether polymeric or otherwise, unless stated to the contrary.In contrast, the term, “consisting essentially of” excludes from thescope of any succeeding recitation any other component, step orprocedure, excepting those that are not essential to operability. Theterm “consisting of” excludes any component, step or procedure notspecifically delineated or listed. The term “or”, unless statedotherwise, refers to the listed members individually as well as in anycombination.

“Composition” and like terms mean a mixture or blend of two or morecomponents.

“Blend,” “polymer blend” and like terms mean a blend of two or morepolymers, as well as blends of polymers with various additives. Such ablend may or may not be miscible. Such a blend may or may not be phaseseparated. Such a blend may or may not contain one or more domainconfigurations, as determined from transmission electron spectroscopy,light scattering, x-ray scattering, and any other method known in theart.

The term “polymer” (and like terms) is a macromolecular compoundprepared by reacting (i.e., polymerizing) monomers of the same ordifferent type. “Polymer” includes homopolymers and copolymers.

In an embodiment, the compositions disclosed herein are phthalate-free.The term “phthalate-free composition,” as used herein, is a compositiondevoid of phthalate or is otherwise free of phthalate. A “phthalate,” isa compound which includes the following structure (I):

wherein R and R′ may be the same or different. Each of R and R′ isselected from a substituted-/unsubstituted-hydrocarbyl group having 1 to20 carbon atoms. As used herein, the term “hydrocarbyl” and“hydrocarbon” refer to substituents containing only hydrogen and carbonatoms, including branched or unbranched, saturated or unsaturated,cyclic, polycyclic, fused, or acyclic species, and combinations thereof.Nonlimiting examples of hydrocarbyl groups include alkyl-, cycloalkyl-,alkenyl-, alkadienyl-, cycloalkenyl-, cycloalkadienyl-, aryl-, aralkyl,alkylaryl, and alkynyl-groups. Each position 3, 4, 5, and 6 may bepopulated by hydrogen or other moiety.

In an embodiment, the compositions disclosed herein are lead-free.

In an embodiment, an acetylated castor component is provided. A “castorcomponent,” as used herein, is a castor oil, a castor wax, or a mixturethereof. The term “castor oil” is a pale yellow-to-colorless viscousliquid obtained from the castor bean/seed of the castor plant Ricinuscommunis. Castor oil is a triglyceride in which from about 85 wt % toabout 95 wt % of the fatty acid chains are ricinoleic acid. A “fattyacid,” as used herein, is a monocarboxylic acid composed of an aliphaticchain containing 4 to 22 carbon atoms with a terminal carboxyl group(COOH). The fatty acid can be saturated or unsaturated, branched orunbranched, and may or may not include one or more hydroxyl group(s).

A nonlimiting compositional representation of castor oil is provided atRepresentation (II) below.

Compositional Representation of Castor Oil (II)

The term “castor wax” is hydrogenated castor oil, and is a hard,brittle, high melting point wax with about 40 wt % to about 95 wt %glyceryl trihydroxystearate. It is produced by the hydrogenation ofcastor oil, typically in the presence of a nickel catalyst. Castor waxis odorless and is insoluble in water. Castor wax may be partially orfully hydrogenated castor oil.

The castor component is acetylated. The term “acetylating” or“acetylation,” as used herein, is the process of introducing an acetylgroup into the molecule of a compound having —OH groups. In other words,acetylation replaces H of the —OH groups with CH₃CO— groups. Acetylationmay also occur with a fatty acid moiety having a hydroxyl group (i.e.,the —OH group at C₁₂ of the ricinoleic acid moiety of a glyceride).Nonlimiting examples of suitable acetylation reagents include aceticanhydride and acetyl chloride. Thus, an “acetylated castor component”(or “ACC”) is a castor component that has been subjected to anacetylation reaction. In other words, an acetylated castor component isthe reaction product of a castor component and an acetylation reagent.In particular, the acetylated castor component may be an acetylatedcastor oil (“ACO”) or an acetylated castor wax (“ACW”) or mixturesthereof. The ACW may be fully or partially hydrogenated.

In an embodiment, the ACC has a hydrogenation efficiency of about 95% to99% The efficiency is defined by the conversion of the unsaturateddouble bonds into saturated bonds of oleic, linoleic and ricinoleic acidpresent in castor oil. Reduction in Iodine value is a good measure ofhydrogenation efficiency. It has been found that hydrogenation of thehydroxyl groups forms a keto-stearic acid. The keto-stearic acid affectsthe amount of insolubles in the final product and correspondingly theclarity of the ACC. Purification (as described below) preferablydecreases or removes any keto-stearic acid formed.

Some, substantially all, or all, of the —OH groups of the castorcomponent may be acetylated. The acetylation results in an acetylatedcastor component having a lower hydroxyl number than the castorcomponent. The acetylated castor component has a hydroxyl number from 0to less than 15, or from 0 to less than 10, or from 0 to less than 5, or0 to less than 2, or 0.

In an embodiment, the castor component is composed solely of glyceryltrihydroxystearate. Consequently, the ACC may be acetylated glyceryltrihydroxystearate. In one embodiment, the acetylated glyceryltrihydroxystearate has a hydroxyl number from 0 to less than 15, or from0 to less than 10, or from 0 to less than 5, or from 0 to less than 2,or 0.

In another embodiment, the acetylated castor wax has a viscosity fromabout 100 mPa·s to less than about 2000 mPa·s at 25° C.

Nonlimiting properties for the castor component and nonlimitingembodiments of the acetylated castor component, and a single phaseacetylated castor component are provided in Table 1 below.

TABLE 1 Single Phase- Acetylated Acetylated Acetylated Castor Oil CastorCastor Wax Castor Wax Properties Castor Oil (ACO) Wax (ACW) (SP-ACW)Melting Point Liq @ RT Liq @ RT 60-87 Liq @ RT Liq @ RT (° C.) Density(g/cc) 0.945-0.965 0.950-0.960 solid 0.950-0.960 0.950-0.960 at 25° C.Acid number <3 1-8 <3 1-8 1-8 (mg KOH/g) Iodine value 82-90 ≧40 <45 <40<40 (gI₂/100 g) Hydroxyl 150-175 0 to less than 5 150-175 0 to less 0 toless Number (mg than 15 than 15 KOH/g) Viscosity 600-900 50 to less than100 to less 100 to less mPa · s (@ 25 C.) 1000 than 2000 than 2000 Wt %≧0.2 <0.2 Insoluble Component* *Removed by Cooling to 15° C. for 1 weekand filtering at 15° C. to 25° C. with 11 μm or larger filter paper

Complete, or substantially complete, acetylation of the ACC yields aliquid plasticizer composition with a viscosity suitable for use withpolymeric resins and vinyl chloride resins in particular. In anembodiment, Applicants have surprisingly discovered a liquid ACW with aviscosity from about 100 mPa·s to less than about 2000 mPa·s at 25° C.In another embodiment, the ACW has a hydroxyl number from 0 to less than15. In a further embodiment, the ACW may also have an iodine number of 0to less than 40 g I₂/100 g.

Applicants also have discovered a liquid ACO with a hydroxyl number from0 to less than 5 which has a viscosity from about 50 mPa·s to less than1000 mPa·s at 25° C. The ACO may also have an iodine number from about40 g I₂/100 g to about 90 g I₂/100 g.

In an embodiment, the acetylated castor component has an acid numberfrom about 0 mg KOH/g to about 8 mg KOH/g.

In an embodiment, the acetylated castor component has an APHA color fromabout 50 to less than about 3000, or from about 50 to less than about1000, or from about 50 to less than about 500, or from about 50 to lessthan about 300.

In an embodiment, the ACC is a single-phase ACC. A “single phaseacetylated castor component” (“SP-ACC”) is any of the foregoing ACCsthat is (1) exposed to a temperature from 5° C. to 50° C., or 15° C.,for at least three hours to one week, (2) subsequently subjected to apurification process (as described below), (3) then is exposed to 15° C.for at least 1 week, and (4) is filtered at 15-25° C. with 11 μm orlarger filter paper which collects less than 0.2 wt % of an insolublecomponent(s) on the filter paper. The SP-ACC is solely (or substantiallysolely) a liquid phase at room temperature. The term “insolublecomponent,” as used herein, is one or more compounds that phase separateout of the ACC over time. The ACC is a liquid at room temperature andthe insoluble component phase separates out of the liquid phase ACC as asolid phase. The insoluble component turns the ACC cloudy, settles tothe bottom and may lead to excessive spew when the ACC is used as aplasticizer. The lower the temperature, the more insolubles are formed.Furthermore, the grade of castor oil or castor wax used for acetylationalso has an effect on the amount of insolubles formed, as well as thecolor of the ACC.

The SP-ACC is prepared by subjecting any of the foregoing ACCs to apurification process. A “purification process,” as used herein, is theapplication of one or more of the following procedures to the ACC: afiltration procedure, a centrifugation procedure, a sedimentationprocedure, treatment with additives [such as silicon dioxide (SiO₂),aluminum oxide (Al₂O₃), activated carbon, Perlite (naturally occurringamorphous siliceous volcanic rock), diatomaceous earth] and combinationsthereof. Any of these procedures may optionally be performed at atemperature from 5° C. to 50° C. and holding at this temperature for atleast 3 hours. The additives may be used to aid the filtration step andmay also result in desirably lighter color of the ACC. The purificationprocess removes, wholly or partially, any insoluble components presentin the ACC and can also result in desirably lighter color. Treatment ofthe ACC with additives, followed by filtration, can also be performed attemperatures as high as 150° C. to result in lighter color, withoutnecessarily decreasing the amount of insolubles. With removal of thesolid phase from the ACC and/or lighter color, the resultant filtratefrom the purification process is the single-phase ACC(SP-ACC). TheSP-ACC is clear and has low, or no, turbidity. The SP-ACC may be anSP-ACW, an SP-ACO, and combinations thereof.

In an embodiment, the amount of insoluble component (if any) present inthe SP-ACC is determined by filtering the SP-ACC at 15° C., over 11 μmor larger filter paper, (the SP-ACC being exposed to 15° C. for at leastone week prior to this filtration). The amount of insoluble componentdeposited on the filter paper is less than 0.2 wt %. Weight percent ofthe insoluble component is based on the total weight of the purifiedACC, (i.e., the total weight of the SP-ACC before filtration over 11 μmor larger filter paper).

In an embodiment, the SP-ACC contains less than 0.2 wt %, or from 0 wt %to less than 0.2 wt % insoluble component after being exposed to 15° C.for at least one week, or at least two weeks, or at least one month, orat least six months, or at least 12 months (or any time durationtherein).

In an embodiment, the SP-ACC contains from about 0 wt % to less thanabout 0.2 wt % insoluble component. A nonlimiting example of an SP-ACCis an SP-ACW and is provided in Table 1 above. The SP-ACC is clear andadvantageously produces no, or substantially no, spew when used as aplasticizer or coplasticizer in polymer compositions.

In an embodiment, the insoluble component is composed of mixedacetylated triglycerides containing at least one saturated fatty acid.Nonlimiting examples of individual components, formed aftersaponification of the insoluble component to fatty acids and methylationto form the esters, are set forth in Table 2 below.

TABLE 2 Nonlimiting examples of individual components of the insolublecomponent(s) after saponification and methylation Component C16:0(Hexadecanoic acid methyl ester, saturated) C18:0 (Octadecanoic acidmethyl ester, saturated, branched) C18:1 (Octadecanoic acid methylester, unsaturated, one double bond) C18:0 (Octadecanoic acid methylester, saturated) C19:0 (Nonadecanoic acid methyl ester, saturated)C18:0 (Octadecanoic acid 12-oxo methyl ester, saturated) C20:0(Eicosanoic acid methyl ester, saturated) C18:0 (Octadecanoic acidmethyl ester, saturated and functionalized —OH) C22:0 (Docosanoic acidmethyl ester, saturated)

In an embodiment, the single phase acetylated castor component has aturbidity from 0 NTU to 50 NTU, or from 1.0 NTU to 50 NTU.

In an embodiment, the single phase acetylated castor component has colorless than 500 APHA, or from 50 APHA to 500 APHA, or from 50 APHA to lessthan 300 APHA.

In an embodiment, the single phase acetylated castor component has ahydroxyl number from 0 to less than 5 as measured in accordance with DIN53402.

In an embodiment, the single phase acetylated castor component has aviscosity less than 2000 mPa·s as measured in accordance with ASTM D 445at 25° C.

In an embodiment, the single phase acetylated castor component has aniodine value of 0 to 3, or 3.

Applicants have surprisingly and unexpectedly discovered a single phaseacetylated castor component (SP-ACC) with (i) a low hydroxyl number,(ii) a low viscosity, (iii) a low turbidity, (iv) low APHA color, andoptionally (v) a low iodine number which yields a plasticizer withexcellent compatibility when added to polymeric resins (and vinylchloride resins in particular). The present SP-ACC is phthalate-free,lead-free and provides a plasticizer that replicates all, orsubstantially all, the properties afforded by phthalate-basedplasticizers.

The single phase acetylated castor component may comprise two or moreembodiments disclosed herein.

In an embodiment, a composition is provided and includes a blend of (i)the SP-ACC and (ii) one or more epoxidized fatty acid ester (EFA). TheSP-ACC may be any SP-ACC (i.e., any SP-ACO, any SP-ACW, and combinationsthereof) as disclosed above with no limit regarding hydroxyl numberand/or viscosity. The term “epoxidized fatty acid ester,” as usedherein, is a compound with at least one fatty acid moiety which containsat least one epoxide group. An “epoxide group” is a three-memberedcyclic ether (also called oxirane or an alkylene oxide) in which anoxygen atom is joined to each of two carbon atoms that are alreadybonded to each other. Nonlimiting examples of suitable epoxidized fattyacid esters include epoxidized soybean oil, epoxidized propylene glycoldioleate, epoxidized palm oil, epoxidized linseed oil, epoxidized fattyacid methyl esters, epoxidized derivatives of each of the foregoing, andany combination of the foregoing.

The epoxidized fatty acid ester can be prepared in a variety of ways.For example, natural oils can be used as the starting material. In thisinstance, the natural oils may be saponified to the fatty acids and thenesterified with alcohols. Next, the low molecular weight esters areepoxidized. The unsaturated ester can be epoxidized with a per-acid.

Alternatively, a glycidyl ester of the fatty acid can be prepared viaepichlorohydrin or related chemicals. In yet another alternate, it ispossible to transesterify the triglyceride with alcohols and thenepoxidize the unsaturated fatty ester with a per-acid.

In an embodiment, the epoxidized fatty acid ester can be any epoxidizedfatty acid C₁-C₁₄ ester, including methyl, ethyl, propyl, butyl, and2-ethylhexyl esters. In a further embodiment, the epoxidized fatty acidester is an epoxide of a fatty acid methyl ester.

A nonlimiting example for the preparation of an epoxide of a fatty acidmethyl ester begins with soy oil, wherein the soy oil is transesterifiedwith methanol to make the methyl ester of the fatty acids in the oil.Glycerol is removed from the reaction products due to insolubility. Asolution of per-acetic acid in ethyl acetate is used to epoxidize thedouble bonds on the fatty acids. The per-acid is kept below 35% per-acidand 35 degrees Celsius to prevent detonation. After completion, theethyl acetate and product acetic acid are removed via vacuum stripping.

In an embodiment, the epoxidized fatty acid ester is epoxidized soybeanoil.

The SP-ACC/EFA mixture may be referred to as a “composition,” “aplasticizer composition,” “a plasticizer,” or “SP-ACC/EFA plasticizer.”The plasticizer composition may include from about 1 wt % to about 99 wt% SP-ACC and from about 99 wt % to about 1 wt % EFA, or from about 30 wt% to about 99 wt % SP-ACC and from about 70 wt % to about 1 wt % EFA(based on the total weight of the plasticizer composition).

A “plasticizer composition” or “plasticizer” is a substance that lowersthe modulus and tensile strength, and increases flexibility, elongation,impact strength, and tear strength of the polymeric resin (typically athermoplastic polymer) to which it is added. A plasticizer may alsolower the melting point of the polymeric resin, lower the glasstransition temperature and enhance processability of the polymeric resinto which it is added.

The plasticizer composition may include one or more SP-ACCs and/or oneor more EFAs. In an embodiment, the plasticizer composition may includean SP-ACC having a hydroxyl number from 0 to less than 15, or from 0 toless than 10, or from 0 to less than 5, or from 0 to less than 2, or 0,and epoxidized soybean oil. In a further embodiment, the SP-ACC of theplasticizer composition may have a hydroxyl number of 0 and theplasticizer composition also includes epoxidized soybean oil.

In an embodiment, the present plasticizer composition is a bio-basedplasticizer composition. A “bio-based plasticizer composition,” as usedherein, is a plasticizer composition composed of a vegetable-derivedmaterial. The ACC and the EFA are each vegetable-derived materials(castor bean and soybean, respectively). A bio-based plasticizercomposition is advantageous because it reduces greenhouse gas emissions,and enables the user to obtain carbon and/or LEED (Leadership in Energyand Environmental Design) credits.

In an embodiment, the plasticizer composition includes a SP-ACW with aviscosity from about 100 mPa·s to about 2000 mPa·s at 25° C. or fromabout 100 to about 500 mPa·s at 25° C. The SP-ACW may also have ahydroxyl number from 0 to less than 15, or 0 to less than 10, or 0 toless than 5, or 0 to less than 2, or 0. The SP-ACW is blended with anyof the foregoing EFAs.

In an embodiment, the plasticizer composition may include a SP-ACO witha hydroxyl number from 0 to less than 15, or from 0 to less than 10, orfrom 0 to less than 5. The SP-ACO may also have a viscosity from 50mPa·s to less than 1000 mPa·s at 25° C. or from about 100 to about 500mPa·s at 25° C. The SP-ACO is blended with any of the foregoing EFAs.

In an embodiment, the plasticizer composition may include an SP-ACC, afirst EFA, and a second EFA. The second EFA is different than the firstEFA. In a further embodiment, the plasticizer composition includes anSP-ACC, ESO, and an epoxidized propylene glycol dioleate. In yet anotherembodiment, the plasticizer composition includes an SP-ACC, ESO, and anepoxidized fatty acid methyl ester.

In an embodiment, the plasticizer composition is a single phase—i.e., aliquid.

Thus, the EFA alone or in combination with the ACC may be subjected toany of the foregoing purification processes used to form the SP-ACC. Inan embodiment, the EFA contains less than about 0.2 wt %, or from 0 wt %to less than about 0.2 wt % insoluble components (when exposed to 15° C.for one week). In another embodiment, the SP-ACC/EFA mixture containsless than 0.2 wt %, or 0 wt % to less than about 0.2 wt % insolublecomponents (when exposed to 15° C. for one week). In another embodiment,an ACC/EFA mixture is purified and contains less than 0.2 wt %, or 0 wt% to less than about 0.2 wt % insoluble components (when exposed to 15°C. for one week). Weight percent is based on the total weight of theplasticizer composition.

Although the composition of this disclosure is preferablyphthalate-free, the plasticizer composition may also comprise otherknown plasticizers including, but not limited to, phthalates (such asdi-isononyl phthalate, diallyl phthalate, di-2-ethylhexyl-phthalate,dioctyl phthalate, diisodecyl phthalate and diisotridecyl phthlate),trimellitates (such as trioctyl trimellitate, triisononyl trimellitateand triisodecyl trimellitate), citrates, benzoates and adipicpolyesters.

The present plasticizer composition may comprise two or more embodimentsdisclosed herein.

The present composition composed of SP-ACC alone or in combination withany EFA may be used in a variety of compositions or products.Nonlimiting examples of suitable applications for the compositioninclude cosmetic compositions/products, food compositions/products, andpolymeric compositions/products, soft thermoplastic polyolefins,profiles (gaskets), films, etc.

The present disclosure provides a polymeric composition. In anembodiment, a polymeric composition is provided which includes apolymeric resin and the present plasticizer composition. The plasticizercomposition may be any SP-ACC, any SP-ACC plasticizer, alone or incombination with any EFA as disclosed herein. Plasticizer compatibilityin the polymeric composition is assessed by visual inspection of moldedor extruded specimens aged at elevated temperatures (e.g., 113° C. or136° C.) for defined lengths of time (e.g., 7 days), or by a loop spewtest on molded specimens aged at a fixed temperature (e.g., 23° C.).Loop spew is measured in accordance with ASTM D 3291: Standard TestMethod for Compatibility of Plasticizers in Poly(vinyl chloride)Plastics Under Compression. The polymeric composition has a loop spewfrom 0-2, or 0-1, or 0 as measured in accordance with ASTM D 3291. Thepolymeric composition contains from about 1 wt % to about 99 wt % of thepolymeric resin and from about 99 wt % to about 1 wt % of theplasticizer composition. The plasticizer composition may include fromabout 1 wt % to 99 wt % SP-ACC and from about 99 wt % to about 1 wt %EFA, or from 30 wt % to about 99 wt % SP-ACC and from about 70 wt % toabout 1 wt % EFA. Weight percent is based on total weight of thepolymeric composition.

In an embodiment, the polymeric composition contains less than 0.2 wt %insoluble components or 0 wt % to less than 0.2 wt % insolublecomponents. Weight percent is based on the total weight of the polymericcomposition.

Nonlimiting examples of suitable polymeric resins include polysulfides,polyurethanes, acrylics, epichlorohydrins, nitrile rubber,chlorosulfonated polyethylene, chlorinated polyethylene,polychloroprene, styrene butadiene rubber, natural rubber, syntheticrubber, EPDM rubber, propylene-based polymers, ethylene-based polymers,and vinyl chloride resins. The term, “propylene-based polymer,” as usedherein, is a polymer that comprises a majority weight percentpolymerized propylene monomer (based on the total amount ofpolymerizable monomers), and optionally may comprise at least onepolymerized comonomer. The term, “ethylene-based polymer,” as usedherein, is a polymer that comprises a majority weight percentpolymerized ethylene monomer (based on the total weight of polymerizablemonomers), and optionally may comprise at least one polymerizedcomonomer.

The term “vinyl chloride resin,” as used herein, is a vinyl chloridepolymer, such as polyvinyl chloride (PVC), or a vinyl chloride copolymersuch as vinyl chloride/vinyl acetate copolymer, vinylchloride/vinylidene chloride copolymer, vinyl chloride/ethylenecopolymer or a copolymer prepared by grafting vinyl chloride ontoethylene/vinyl acetate copolymer. The resin composition can also includea polymer blend of the above-mentioned vinyl chloride polymer or vinylchloride copolymer with other miscible or compatible polymers including,but not limited to, chlorinated polyethylene, thermoplasticpolyurethane, olefin polymers such as a methacryl polymer oracrylonitrile-butadiene-styrene polymer (ABS resin).

In an embodiment, the vinyl chloride resin is polyvinyl chloride (PVC).

In an embodiment, the polymeric composition is a thermoplasticcomposition. A “thermoplastic composition,” as used herein, is apolymeric composition (1) that has the ability to be stretched beyondits original length and retract to substantially its original lengthwhen released and (2) softens when exposed to heat and returns tosubstantially its original condition when cooled to room temperature.

In an embodiment, the polymeric composition includes the polymeric resinand a plasticizer including one or more SP-ACC, optionally one or moreEFA, and optionally a second EFA.

In an embodiment, the polymeric composition includes PVC, a SP-ACC andoptionally an EFA. The polymeric composition has a Shore hardness fromabout D10 to about D70, or from about D20 to about D60.

In an embodiment, the plasticizer composition has a solution temperaturefrom about 140° C. to about 200° C. as measured in accordance with DIN53408. Applicants have surprisingly discovered that the plasticizercomposition composed of SP-ACC and an EFA unexpectedly provides aplasticizer with low viscosity and low volatility, which is particularlysuitable for high temperature wire and cable applications, and whichdoes not migrate out of a thermoplastic polymer in which it isincorporated. In addition, the solution temperature (of 140° C.-200° C.)for the present plasticizer composition is similar to the solutiontemperature of conventional high molecular weight plasticizers(typically between about 140° C. and about 180° C.). Moreover, theviscosity of the present plasticizer composition is less than theviscosity of conventional high molecular weight plasticizers, such asadipic polyester plasticizers. For example, adipic polyesterplasticizers, known commercially as Ultramoll® IV and Ultramoll® IIIadipic polyesters (products of Lanxess) have very high viscosity(approximately 6000 to 6500 mPa·s at 25° C.). It is known that the lowerthe viscosity of a plasticizer, the faster is its uptake into PVCpowder. Hence, the present plasticizer compositions are absorbed intoPVC at a faster rate than adipic polyester plasticizers, and eventrimellitates of lower or similar viscosity. The present plasticizercomposition exhibits an unexpected synergy between low viscosity andhigh molecular weight and yields a phthalate-free, safe, plasticized PVCwith physical, chemical, and mechanical properties that meet and/orexceed the properties of PVC resins plasticized with conventional adipicpolyester plasticizers or conventional phthalate-based plasticizers orconventional trimellitate-based plasticizers. Especially noteworthy isthe retention of tensile properties exhibited by the present compositionafter oven aging for 168 hours at temperatures as high as 136° C.

The present polymeric composition exhibits the same, or better,flexibility and/or elongation when compared to polymer resins containingconventional adipic polyester, phthalate, and/or trimellitateplasticizers. In an embodiment, the present polymeric composition is ablend of PVC and a SP-ACC/EFA plasticizer and has a Shore hardness fromabout D10 to about D70, or from about D20 to about D60. Shore hardnessis measured in accordance with ASTM D 2240.

In an embodiment, the polymeric composition is composed of a blend ofPVC and the SP-ACC/EFA plasticizer. The polymeric composition is moldedinto a plaque. The plaque has a tensile strength retention greater thanabout 70%, or greater than about 75%, after 168 hours heat aging at 113°C. as measured on dogbones cut from 30 mil thick plaques in accordancewith UL 1581 and ASTM D 638.

In an embodiment, the polymeric composition is composed of a blend ofPVC and the SP-ACC/EFA plasticizer. The polymeric composition is moldedinto a plaque. The plaque has a tensile strength retention greater thanabout 70% after 168 hours heat aging at 136° C. as measured on dogbonescut from 30 mil thick plaques in accordance with UL 1581 and ASTM D 638.

In an embodiment, the present polymeric composition is composed of ablend of PVC and the SP-ACC/EFA plasticizer composition. The polymericcomposition is molded into a plaque. The plaque has a tensile elongationretention greater than about 40% after 168 hours heat aging at 113° C.as measured on 30 mil thick plaques in accordance with UL 1581 and ASTMD 638.

In an embodiment, the present polymeric composition is composed of ablend of PVC and the SP-ACC/EFA plasticizer composition. The polymericcomposition is molded into a plaque. The plaque has a tensile elongationretention greater than about 40% after 168 hours heat aging at 136° C.as measured on 30 mil thick plaques in accordance with UL 1581 and ASTMD 638.

The tensile strength and tensile elongation is measured for (i) unagedand (ii) heat aged dogbone specimens cut from compression molded plaquesin accordance with ASTM D-638.

Any of the foregoing polymeric compositions may include one or more ofthe following additives: a filler, an antioxidant, a flame retardant(antimony trioxide, molybdic oxide and alumina hydrate), a heatstabilizer, an anti-drip agent, a colorant, a lubricant, a low molecularweight polyethylene, a hindered amine light stabilizer (having at leastone secondary or tertiary amine group) (“HALS”), UV light absorbers(such as o-hydroxyphenyltriazines), curing agents, boosters andretardants, processing aids, coupling agents, antistatic agents,nucleating agents, slip agents, viscosity control agents, tackifiers,anti-blocking agents, surfactants, extender oils, acid scavengers, metaldeactivators, and any combination thereof.

In an embodiment, the present polymeric composition includes a filler.Nonlimiting examples of suitable fillers include calcium carbonate,calcined clay, whiting, fuller's earth, magnesium silicate, bariumsulfate, calcium sulfate, strontium sulfate, titanium dioxide, magnesiumoxide, magnesium hydroxide, calcium hydroxide, hydrophilic fumed silica,hydrophobic (surface treated) fumed silica, and any combination of theforegoing. Nonlimiting examples of calcined clay are Satintone® SP-33and Polyfil® 70.

In an embodiment, the present polymeric composition includes anantioxidant. Nonlimiting examples of suitable antioxidants includehindered phenols such astetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydro-cinnamate)]methane;bis[(beta-(3,5-ditert-butyl-4-hydroxybenzyl)-methylcarboxyethyl)]sulphide,4,4′-thiobis(2-methyl-6-tert-butylphenol),4,4′-thiobis(2-tert-butyl-5-methylphenol),2,2′-thiobis(4-methyl-6-tert-butylphenol), and thiodiethylenebis(3,5-di-tert-butyl-4-hydroxy)hydrocinnamate; phosphites andphosphonites such as tris(2,4-di-tert-butylphenyl)phosphite anddi-tert-butylphenyl-phosphonite; thio compounds such asdilaurylthiodipropionate, dimyristylthiodipropionate, anddistearylthiodipropionate; various siloxanes; polymerized2,2,4-trimethyl-1,2-dihydroquinoline,n,n′-bis(1,4-dimethylpentyl-p-phenylenediamine), alkylateddiphenylamines, 4,4′-bis(alpha, alpha-dimethylbenzyl)diphenylamine,diphenyl-p-phenylenediamine, mixed di-aryl-p-phenylenediamines, andother hindered amine anti-degradants or stabilizers. Nonlimitingexamples of suitable antioxidants include Topanol® CA, Vanox® 1320,Irganox® 1010, and Jrganox® 1076. The antioxidant or antioxidants may beadded to the plasticizer composition of this disclosure. Antioxidantscan be used in amounts of 0.01 to 5 wt % based on the weight of thecomposition.

In an embodiment, the present polymeric composition includes a heatstabilizer. Nonlimiting examples of suitable heat stabilizers includelead-free mixed metal heat stabilizers, lead stabilizers, organic heatstabilizers, epoxides, salts of monocarboxylic acids, phenolicantioxidants, organic phosphites, and/or betadiketones. A nonlimitingexample of suitable betadiketones is dibenzoylmethane. A nonlimitingexample of suitable dibenzoylmethane is Rhodiastab® 83. Nonlimitingexamples of suitable lead-free mixed metal heat stabilizers includeMark® 6797, Mark® 6776 ACM, Mark® 6777 ACM, Therm-Chek® RC215P,Therm-Chek® 7208, Naftosafe® EH-314, Baeropan® MC 90400 KA, Baeropan® MC90400 KA/1, Baeropan® MC8553 KA-ST 3-US, Baeropan® MC 9238 KA-US,Baeropan® MC 90249 KA, and Baeropan® MC 9754 KA. The heat stabilizer orheat stabilizers may be added to the plasticizer composition of thisdisclosure. Heat stabilizers can be used in amounts of 0.1 to 10 wt %based on the weight of the composition.

In an embodiment, the present polymeric composition includes alubricant. Nonlimiting examples of suitable lubricants include stearicacid, metal salts of stearic acid, wax, and polyethylene glycols. Thelubricants may be used alone or in combination.

In an embodiment, the present polymeric composition includes aprocessing aid. Nonlimiting examples of suitable processing aids includemetal salts of carboxylic acids such as zinc stearate or calciumstearate; fatty acids such as stearic acid, oleic acid, or erucic acid;fatty amides such as stearamide, oleamide, erucamide, or N,N′-ethylenebis-stearamide; polyethylene wax; oxidized polyethylene wax; polymers ofethylene oxide; copolymers of ethylene oxide and propylene oxide;vegetable waxes; petroleum waxes; non ionic surfactants; andpolysiloxanes. Processing aids can be used in amounts of 0.05 to 5 wt %based on the weight of the composition.

The polymeric compositions are generally prepared according toconventional dry blend or wet blend methods known to those skilled inthe art of PVC compounding. The mixtures obtained from the blendingprocess can be further compounded with a mixer such as a Banbury batchmixer, a Farrel Continuous Mixer, or a single or twin screw extruder.

In an embodiment, the present polymeric composition is made byabsorption of the plasticizers of this disclosure in PVC powder to makea dry blend. Any suitable method/apparatus may be used to make the dryblend including, but not limited to, a Henschel mixer or a ribbonblender. The polymeric composition may contain other additives inaddition to the PVC and the plasticizer. The dry blend may then befurther compounded (via melt extrusion for example) and formed into anydesired shape (film, pellet, etc.).

With an optimal stabilizer and antioxidant package, the presentpolymeric compositions are suitable for applications requiring long termdry or wet insulation resistance testing at elevated temperatures, andother demanding applications where temperatures are as high as 136° C.

The present polymeric composition(s) may comprise two or moreembodiments disclosed herein.

The surprising properties of flexibility, low plasticizer volatility,low migration, low viscosity and/or high solution temperature exhibitedby the present polymeric composition make it well suited for wire andcable coating applications (jackets, insulation), and high temperaturewire/cable applications in particular. Accordingly, the presentdisclosure provides a coated metal conductor. In an embodiment, a coatedmetal conductor is provided and includes a metal conductor and a coatingon the metal conductor. The coating is composed of the present polymericcomposition which includes the polymeric resin and the presentplasticizer composition. The polymeric resin of the coating may be anypolymeric resin disclosed herein. The plasticizer composition may be anyplasticizer composition composed of one or more SP-ACC, alone or blendedwith one or more EFA as disclosed herein.

A “metal conductor,” as used herein, is at least one metal wire and/orat least one metal cable. The coated metal conductor may be flexible,semi-rigid, or rigid. The coating (also referred to as a “jacket” or a“sheath” or “insulation”) is on the metal conductor or on anotherpolymeric layer around the conductor. The coating includes the presentcomposition. The composition may be any composition as disclosed herein.As used herein, “on” includes direct contact or indirect contact betweenthe coating and the metal conductor. “Direct contact” is a configurationwhereby the coating immediately contacts the metal conductor, with nointervening layer(s) and/or no intervening material(s) located betweenthe coating and the metal conductor. “Indirect contact” is aconfiguration whereby an intervening layer(s) and/or an interveningstructure(s) and/or intervening material(s) is/are located between themetal conductor and the coating. The coating may wholly or partiallycover or otherwise surround or encase the metal conductor. The coatingmay be the sole component surrounding the metal conductor.Alternatively, the coating may be one layer of a multilayer jacket orsheath encasing the metal conductor.

In an embodiment, the polymeric resin is a vinyl chloride resin such asPVC as discussed above. The PVC is blended with the plasticizercomposition to form the coating. The coating may include additionalcomponents. In an embodiment, the coating includes from about 1 wt % toabout 99 wt % or from about 20 wt % to about 80 wt %, or from about 30wt % to about 70 wt % PVC and from 99 wt % to about 1 wt %, or fromabout 80 wt % to about 20 wt %, or from about 70 wt % to about 30 wt %plasticizer composition. In a further embodiment, the coating containsfrom about 30 wt % to about 90 wt % PVC and from about 70 wt % to about10 wt % of the plasticizer composition.

The plasticizer composition may be any plasticizer composition disclosedherein. In an embodiment, the SP-ACC present in the coating comprisesless than 0.2 wt % insoluble components. The SP-ACC present in thecoating may have a hydroxyl number from 0 to less than 15, or from 0 toless than 10, or from 0 to less than 5, or from 0 to less than 5, or 0.

The coating may have any of the properties as discussed above for thepresent composition. In an embodiment, the coated conductor passes theheat test as measured in accordance with UL-1581. In another embodiment,the plasticizer composition in the coating has a solution temperaturefrom about 140° C. to about 200° C. In another embodiment, the coatinghas a Shore hardness from about D10 to about D70 as measured inaccordance with ASTM D 2240.

Nonlimiting examples of suitable coated metal conductors includeflexible wiring such as flexible wiring for consumer electronics, apower cable, a power charger wire for cell phones and/or computers,computer data cords, power cords, appliance wiring material, buildingwire, automotive wire, and consumer electronic accessory cords.

The present coated conductor may comprise two or more embodimentsdisclosed herein.

The coated conductor, such as a coated wire or a coated cable (with anoptional insulation layer), with a jacket comprising the compositiondisclosed herein can be prepared with various types of extruders, e.g.,single or twin screw types. A description of a conventional extruder canbe found in U.S. Pat. No. 4,857,600. An example of co-extrusion and anextruder can be found in U.S. Pat. No. 5,575,965. A typical extruder hasa hopper at its upstream end and a die at its downstream end. The hopperfeeds into a barrel, which contains a screw. At the downstream end,between the end of the screw and the die, there is a screen pack and abreaker plate. The screw portion of the extruder is considered to bedivided up into three sections, the feed section, the compressionsection, and the metering section, and two zones, the back heat zone andthe front heat zone, the sections and zones running from upstream todownstream. In the alternative, there can be multiple heating zones(more than two) along the axis running from upstream to downstream. Ifit has more than one barrel, the barrels are connected in series. Thelength to diameter ratio of each barrel is in the range of about 15:1 toabout 30:1.

The wire and cable constructions (i.e., a coated metal conductor) ofthis disclosure are made by extruding the present composition onto theconductor or onto the bundle of insulated conductors to form a coating(or a jacket) around the insulated conductors. The thickness of thejacket or insulation depends on the requirements of the desired end useapplication. Typical thickness of the jacket or insulation is from about0.010 inches to about 0.200 inches, or from about 0.015 inches to about0.050 inches. The present composition may be extruded into the jacketfrom previously made composition. Usually the present composition is inthe form of pellets for easy feeding into the extruder. The wire andcable jacket or insulation may be extruded directly from the compoundingextruder without going through the separate step of pelletizing thepresent composition. This one-step compounding/extrusion process wouldeliminate one heat history step for the composition.

In an embodiment, a nylon layer may also be extruded over theinsulation, such as in conventional THHN, THWN and THWN-2 constructions.

Nonlimiting examples of embodiments of the present disclosure areprovided below.

In an embodiment, a method for making a coated conductor is provided.Such method comprises purifying a plasticizer composition comprising anacetylated castor component and optionally an epoxidized fatty acidester, and forming a plasticizer composition with less than about 0.2 wt% insoluble components. The purification may occur by way of filtrationand/or centrifugation of the plasticizer composition. The method furthercomprises mixing the plasticizer composition with a polymeric resin toform a polymeric composition. The method includes coating a metalconductor with the polymeric composition and a forming a coatedconductor.

The disclosure provides a process. The process includes purifying anacetylated castor component and forming a single phase castor componenthaving less than 0.2 wt % insoluble component(s) after exposure to 15°C. for one week.

In an embodiment, the purification step of the process is selected fromfiltrating, centrifugating, sedimenting, treating with additives [suchas silicon dioxide (SiO₂), aluminum oxide (Al₂O₃), activated carbon,Perlite (naturally occurring amorphous siliceous volcanic rock),diatomaceous earth], and combinations thereof.

In an embodiment, the process includes exposing, prior to the purifying,the acetylated castor component to a temperature from 5° C. to 50° C.for at least three hours, or for at least three hours to one week, or atleast three hours to two weeks, or at least three hours to one month, orat least three hours to six months, or at least three hours to 12 months(or any value therein).

In an embodiment, the process includes treatment of the acetylatedcastor component with additives [such as silicon dioxide (SiO₂),aluminum oxide (Al₂O₃), activated carbon, Perlite (naturally occurringamorphous siliceous volcanic rock), diatomaceous earth], followed byfiltration, at temperatures as high as 150° C. to result in lightercolor, without necessarily decreasing the amount of insolubles.

In an embodiment, the process includes blending the single phaseacetylated castor component with an epoxidized fatty acid ester andforming a plasticizer composition.

In an embodiment, the process includes blending the plasticizercomposition with a polymeric resin, and forming a polymeric compositionhaving a loop spew value from 0-2, or 0-1, or 0.

In an embodiment, the process includes coating the polymeric compositionon a metal conductor and forming a coated conductor. The polymericcomposition includes a polymeric resin and the plasticizer composition.

The process may comprise two or more embodiments disclosed herein.

Test Methods

Acid number (or “acid value”) is a measure of the amount of free acidpresent in a compound. The acid number is the number of milligrams ofpotassium hydroxide required for the neutralization of free acid (fattyacid and/or other acid such as acetic acid, for example) present in onegram of a substance. The acid number is determined in accordance withGerman Standard DIN 53402 (mg KOH/g).

APHA color is measured using Color Quest XE colorimeter, available fromHunterLab, or equivalent; 20-mm transmission cell; HunterLab Universalsoftware, version 4.10 or equivalent; Black and White color referencetitles available from HunterLab, or equivalent; the measured APHA colorvalue of deionized (DI) water is zero.

Density at 25° C. is determined in accordance with German Standard DIN51 757 (g/cm³).

Dynamic storage modulus (G′) and Glass transition temperature (Tg) aredetermined by dynamic mechanical analysis (DMA) using a TA InstrumentAR1000N Rheometer having DMA fixtures. The specimen is in the form of arectangular solid and tested in tension mode. The temperature is variedfrom −100° C. to +160° C. at a ramp rate of 5° C./min, and the testfrequency is held constant at 6.283 rad/s (1 Hz). The storage and lossmodulus of the sample, as well as the tan delta, are measured as afunction of the temperature. The glass transition temperature (Tg) isdetermined from the peak tan delta measurement. Dynamic storage modulus(G′) at −20° C. is used as a measure of low temperature flexibility. Thestorage and loss modulus of viscoelastic materials are measures of thestored energy (representing the elastic portion) and the energydissipated as heat (representing the viscous portion).

Hydroxyl Number (or hydroxyl value) is an indication of the degree ofacetylation and is a measure of the number of hydroxyl groups present ina polymer. The hydroxyl number is the number of milligrams of potassiumhydroxide required to neutralize the hydroxyl groups in one gram ofpolymer. The hydroxyl number is determined in accordance with GermanStandard DIN 53 240 (mg KOH/g).

Iodine Number is an indication of the degree of hydrogenation and isdetermined in accordance with German Einheitsmethode DGF C-V 11a (53) (gI₂/100 g).

Loop spew is measured in accordance with ASTM D 3291 which determinesthe compatibility of plasticizers in poly(vinyl chloride) plastics byrating the amount of plasticizer that spews due to compressional stressset up inside a 180° loop bend. Briefly, using this method, testspecimens of plasticized poly(vinyl chloride) sheet are bent through anarc of approximately 180° and secured in a jig designed to hold them inthe desired conformation. The specimens are held at controlledtemperature (i.e., 23° C.) and, at specified intervals of time, aspecimen is removed, bent 180° in the opposite direction, and the formerinside of the loop is examined for evidence of plasticizer spew byvisual inspection and by wiping the area with a dry index finger. Table3 shows the ranking of values for loop spew.

TABLE 3 Amount of Description (Spew/Migration level) exudate RankingCompletely dry in loop (no visible evidence in loop) none 0 (i.e., nospew or no migration) Slippery with slight amounts of oily substancesslight 1 on the inside of the loop (i.e., low spew or low migration)Slippery with moderate amounts of oily substances moderate 2 on theinside of the loop (i.e., moderate spew or moderate migration) Slipperywith large amounts of oily substances heavy/ 3 on the inside of the loopdripping (i.e., high spew or high migration)

Plasticizer compatibility in the polymeric composition is also assessedby visual inspection of molded or extruded specimens aged at elevatedtemperatures (e.g., 113° C. or 136° C.) for defined lengths of time(e.g., 7 days). The extruded specimens may be in the form of a wire(i.e., insulation extruded over conductor).

Shore hardness is determined in accordance with ASTM D 2240.

Solution Temperature is the temperature at which a heterogeneous mixtureof plasticizer and a PVC resin is observed to change to a single phase.Solution temperature is determined by immersing 1 gram PVC in 20 gramsof plasticizer and increasing the temperature stepwise until the PVC isseen to be completely dissolved by observation under a microscope, inaccordance with German Standard DIN 53 408 (° C.).

Surface smoothness of coated conductors (extruded wires) is measuredusing a surface roughness measuring apparatus made by Mitutoyo of Japan,in accordance with ANSI/ASME B46.1.

Temperature of 5% mass loss (° C.) is determined using TG/DTA 220. Theplasticizer specimen is heated from room temperature up to 600° C. at 10K/min under inert gas purge, and the appearing mass loss and thermaleffects are recorded in thermograms. The higher the temperature for 5%mass loss, the lower the volatility.

Tensile strength and tensile elongation (at 2 inch/min) on unagedspecimens, on specimens aged at 113° C. or at 136° C. for 168 hours, isdetermined in accordance with ASTM D 638 either on dogbones cut frommolded plaques or tubular insulations removed from coated conductors(extruded wires).

Turbidity is measured using a LaMotte model 2020i turbidity meter, whichmeasures both the scattering and attenuation of light. This ISO modelhas a light emitting diode (LED) with wavelength of 860 nm and spectralbandwidth less than or equal to 60 nm. It uses a light detector placedat 90 degrees to the light source to measure scattered light and adetector at 180° to measure light attenuation. A third detector measuresthe intensity of the light source. This instrument is programmed to uselight attenuation at high turbidities and light scattering at lowturbidities. The measurements are made in nephelometric turbidity units(NTU), which is a measure of the cloudiness, or conversely clarity, of aliquid. Turbidity is measured by detecting and quantifying thescattering of light by a liquid or a suspension. Turbidity is measuredby the attenuation of a light beam or the scattering of that light beam.Liquid to be measured for turbidity is poured into an opticallytransparent and non-distorting glass 10-ml vial, which is then insertedinto the instrument and closed with a covering lid. The instrument firstreads a blank vial, which is removed, then the vial containing thesample is inserted, and a measured value in the units chosen (NTU) isreported.

The term “UL 1581” is Underwriters Laboratories Reference Standard forElectrical Wires, Cables, and Flexible Cords. UL 1581 contains specificdetails for conductors, insulation, jackets and other coverings, and formethods of sample preparation, specimen selection and conditioning, andfor measurement and calculation that are required in wire and cablestandards.

Viscosity is determined in accordance with Standard ASTM D 445,Brookfield-Viscosimeter at 25° C. and/or 40° C.

Volume resistivity (Ohm-cm) at 23° C., with 500 volts direct current, ismeasured in accordance with ASTM D 257. Specimens of 3.5 inch diameterare cut from 40 mil thick molded plaques and tested using a HewlettPackard 16008A Resistivity Cell connected to a Hewlett Packard 4329AHigh Resistance Meter.

Water content is determined in accordance with German Standard DIN 51777(%).

Weight Retained (%) after 7 Days at 136° C. is measured on specimens of1.25 inch diameter that are cut from 30 mil thick molded plaques.

By way of example, and not by limitation, examples of the presentdisclosure are provided.

EXAMPLES A. Single Phase Acetylated Castor Component Example 1 SinglePhase Acetylated Castor Wax Sample (SP-ACW4)

Preparation and Separation of Insoluble Components by Filtration

Castor wax (728.5 g) and acetic anhydride (270 g) are charged in a 2 Lflask. The flask is fixed with mechanical stirrer and commondistillation glassware in a preheated bath of 115° C. The temperature ismaintained at 115° C. over 6 hours. Vacuum from 800 to 150 mbar is usedto remove residual acetic acid at a bath temperature of 115° C. Ayellow, liquid product (ACW4) is obtained. The properties of ACW 4 areas follows: Density (g/cc) at 25° C.=0.951; Acid number (mg KOH/g)=1.4;Iodine value (gI2/100 g)=3; Hydroxyl Number (mg KOH/g)=3.7; Viscosity(mPa·s) @ 25° C./40° C.=330/145; Solution Temperature (° C.)=194.5;Water content (wt %)=0.013.

This liquid product (ACW4) is clear immediately after the synthesis. A100 g sample is kept for one week at 15° C. and purified using porousfilter paper [comparable to Whatman Grade 43; 16 microns]. A slimyproduct (0.36 wt %) is separated. The separated products are saponified,methylated and injected in a GC/MS system. The compositions areidentified using the best match of the NIST 2000 library (see Table 4below).

TABLE 4 Compositions of unfiltered liquid phase and of the separatedproduct (deposit) after saponification and methylation Area % of totalArea % (Liquid RT of total Phase- min Component (Deposit) ACW4) 18.47C16:0 (Hexadecanoic acid methyl ester, 2.2 1.6 saturated) 19.44 C18:0(Octadecanoic acid methyl ester, 0.1 0.1 saturated, branched) 20.24C18:1 (Octadecanoic acid methyl ester, 0.4 0.5 unsaturated, one doublebond) 20.38 C18:0 (Octadecanoic acid methyl ester, 36.4 15.9 saturated)21.27 C19:0 (Nonadecanoic acid methyl ester, 0.1 0.1 saturated) 21.98C18:0 (Octadecanoic acid 12-oxo methyl 8.2 4.5 ester, saturated) 22.13C20:0 (Eicosanoic acid methyl ester, 1.5 0.6 saturated) 22.65 C18:0(Octadecanoic acid methyl ester, 50.8 76.7 saturated and functionalized—OH) 23.75 C22:0 (Docosanoic acid methyl ester, 0.3 — saturated)

The results show that the separated product is a mixture of mixedacetylated triglycerides containing at least one saturated fatty acid(mainly octadecanoic acid).

The purified product (SP-ACW4) is clear, and does not become cloudy evenafter more than 14 months at room temperature (20° C.-26° C.), unlikethe unfiltered material (ACW4). After exposure to 15° C. for one week,the SP-ACW4 is filtered over 11 μm or larger filter paper. Less than 0.2wt % insoluble component is collected on the filter paper. Table 5 belowsets forth the properties for SP-ACW4.

TABLE 5 Properties for SP-ACW4 Properties SP-ACW4 Melting Point (° C.)Liq @ RT Density (g/cc) at 25° C. 0.950-0.960 Acid number (mg KOH/g) 1-8Iodine value (gI₂/100 g) <40 Hydroxyl Number (mg KOH/g) 0 to less than15 Viscosity mPa · s (@ 25C) 100 to less than 2000 Wt % InsolubleComponent <0.2

Example 2A Single Phase Acetylated Castor Wax Sample (SP-ACW5(a))

Preparation of Insoluble Components by Centrifugation

The properties of ACW 5 are as follows: Density (g/cc) at 25° C.=0.954;Acid number (mg KOH/g)=2.3; Iodine value (gI2/100 g)=1.5; HydroxylNumber (mg KOH/g)=0; Viscosity (mPa·s) @ 25° C.=348; Water content (wt%)=0.043. Acetylated castor wax (ACW5) is centrifuged at 20° C. and 5000g-force for 8 minutes to precipitate denser insoluble components. Sincethe centrifuge required approximately 1 minute to reach full speed, thisis considered equivalent to a full-scale disk stack centrifuge inproduction operating at 17,000 g-force with a practical residence timeof 124 seconds. Waxy sediment is formed which amounts to 1.33% of theoriginal volume. The starting turbidity of this feed suspension measures235 NTU. Supernatant liquid is decanted, and its turbidity measures 192NTU, reflecting the precipitation of more dense insoluble solids.

Centrifugation of ACW5 is repeated at 5000 g-force and 20° C. for 90minutes. The resulting sediment constitutes 3.67% of the startingvolume, and the turbidity of decanted liquid SP-ACW5(a) measures 38.3NTU.

Example 2B Single Phase Acetylated Castor Wax Sample (SP-ACW5(b))

Separation of Insoluble Components by Filtration

Acetylated castor wax (ACW5) is filtered at 20° C. to remove insolublecomponents using Pall-Seitz composite, lenticular filter medium gradeK100. After 20 minutes, 35 g of filtrate containing practically nosuspended solids is collected from the 47-mm diameter filter disk usinga maximum differential pressure of 30 psi. The turbidity of thisfiltrate SP-ACW5(b) measures 1.8 NTU compared to 235 NTU for theoriginal feed suspension. The color (APHA−20 mm) of this filtrateSP-ACW5(b) measures 256.

Example 3 Single Phase Acetylated Castor Wax Sample (SP-ACW6)

Preparation and Separation of Insoluble Components by Filtration at 15°C.

A 50 ml glass bottle is filled with ACW5 that is pre-heated to 60° C.overnight and homogenized in a quart-sized bottle. The bottle is filledfrom the 5-gallon pail of Example 2 and is stored unfiltered on thelaboratory bench-top. The 50-ml bottle is kept in a 15° C. water bathfor 7 days. Noticeable haze is found to appear after about 1 hour atthis temperature. After 7 days, the liquid is filtered under nitrogenpressure with a 1.2 μm Whatman GF/C glass microfiber filter to produceSP-ACW6. The amount of insolubles collected is measured to be about 1.82wt %. The purified ACW6 (SP-ACW6) is exposed to 15° C. for one week,then filtered over 11 μm (or larger) filter paper which collects lessthan 0.2 wt % insoluble component.

Examples 4 to 6 Single Phase Acetylated Castor Wax Samples (SP-ACW7,SP-ACW8, SP-ACW9)

Preparation and Removal of Color by Contact with Additives andFiltration

Acetylated castor wax (ACW5) is heated to 50° C. A different additive isadded to a respective separate sample of ACW5: 5 wt % of SiO₂ (ACW7), 5wt % Al₂O₃ (ACW8), and 5 wt % activated carbon (ACW9). Each mixture isstirred overnight and subsequently filtered using Whatman QualitativeFilter Paper Grade 1 (11 μm). The color (APHA−20 mm) is measured usingColor Quest XE from Hunter Lab. The APHA value for deionized water is 0.The experimental results are summarized Table 6. All three additives areeffective at removing color from ACW5, resulting in substantiallylighter color, with SiO₂ performing the best.

TABLE 6 Treatment of acetylated castor wax with additives to decreasecolor Ex. 4 Ex. 5 Ex. 6 ACW5 (SP-ACW7) (SP-ACW8) (SP-ACW9) TreatmentUn-treated SiO₂ Al₂O₃ Activated (activated, Carbon neutral) Color 398215 322 279 (APHA-20 mm

B. Thermoplastic Compositions: Blends of PVC & Plasticizer Composition

Thermoplastic compositions composed of blends of polyvinylchloride (PVC)with various plasticizer compositions and additives are prepared asshown in Table 7 below.

TABLE 7 Thermoplastic Compositions Blend 7 (w/ Blend 8 (w/ ACW4 SP-ACW4plasticizer) plasticizer) PVC 62.3 62.3 ACW Plasticizer 15.0 15.0 Clay6.4 6.4 ESO Plasticizer 15.0 15.0 Baeropan ® MC 1.0 1.0 90249 KAIrganox ® 1076 0.3 0.3 Baeropan ® MC 90249 KA = heat stabilizer(Baerlocher) Clay = Satintone ® SP-33 clay filler (New England Resins &Pigments Corp.) ESO = PLAS-CHEK ® 775 epoxidized soybean oil (Ferro)Irganox ® 1076 = hindered phenolic antioxidant (Ciba Chemicals) PVC =polyvinyl chloride homopolymer (OxyVinyls ® 240F) Values = wt % based ontotal weight of composition *Wt % based on weight of total plasticizer

C. Thermoplastic Compositions 7 and 8 (Blends 7 and 8)

The following procedure is used to prepare the Blends 7 and 8:

-   -   Preheat the ACW and ESO plasticizers to 60° C. for at least 60        minutes, shake before use and mix together to make the        plasticizer composition    -   Weigh the individual ingredients    -   First make ‘dry blends’ by soaking the plasticizer composition        into PVC powder, and then make melt mixtures    -   The following procedure is used for preparation of ‘dry blends’:        -   (a) Make “solids mixture” by mixing everything (except            plasticizer composition and filler) in a container using            spatula.        -   (b) Use “40 cm³” Brabender mixing bowl with sigma blades at            90° C. and 40 rpm.        -   (c) After 2 minute warm-up, add the solids mixture. Mix for            30 seconds.        -   (d) Add plasticizer composition. Mix for 360 seconds (6            minutes).        -   (e) Add clay filler. Mix for 60 seconds.        -   (f) Stop and remove “dry blend”.    -   The ‘dry blends’ are subsequently melt mixed using the following        procedure:        -   (a) Use “40 cm³” Brabender mixing bowl with cam rotors at 40            rpm setting.        -   (b) Add ‘dry blend’, and mix at 180° C. for 2 minutes.

The blend compositions from the mixing bowl are compression molded at180° C. for 5 minutes. Specimens are cut from 30 mil thick moldedplaques for testing of all properties except volume resistivity. Thehardness, weight, tensile strength/elongation (at 2 inch/min) aremeasured on unaged specimens and specimens aged at 113° C. or 136° C.for 168 hours, that have been cut from the 30 mil thick plaques. Theheat aged molded specimens are also examined visually for evidence ofexudate (spew) at the surface. Loop spew is measured on specimens agedat room temperature for 48 hours. Volume resistivity is measured onspecimens cut from 40 mil thick molded plaques. The results are given inTable 8.

Table 8 provides properties for the various thermoplastic compositions.

TABLE 8 Plasticizer Color of Blend Com- Melt Shore TSR TSR TER TER WtSpew Spew Spew Vol # position Blend (D) TS 113° C. 136° C. TE 113° C.136° C. Ret. 113° C. 136° C. RT Res 7 ACW4 Cream 38.5 ± 0.4 3676 ± 112 99 ± 7  94 ± 4 291 ± 0  96 ± 10 86 ± 2 99.7 None None 3 4.37E+15 (50)ESO (50) 8 SP-ACW4 Cream 36.4 ± 0.6 3644 ± 113 100 ± 6 101 ± 3 298 ± 1995 ± 11 86 ± 5 99.7 None None 2 4.05E+15 (50) ESO (50) Shore (D) = ShoreD hardness ASTM D 2240 RT = Room temperature Spew 113° C. = Exudate(spew) on surface after 7 days at 113° C. Spew 136° C. = Exudate (spew)on surface after 7 days at 136° C. Spew RT = Loop Spew on surface after48 hours at room temperature (RT) TE = Tensile elongation (%), unagedspecimen, ASTM D 638 TER = Tensile elongation retention (%), ASTM D 638TER 113° C. = Tensile elongation retention (%), specimen aged at 113° C.for 168 hours TER 136° C. = Tensile elongation retention (%), specimenaged at 136° C. for 168 hours TS = Tensile strength (psi), unagedspecimen, ASTM D 638 TSR = Tensile strength retention (%), ASTM D 638TSR 113° C. = Tensile strength retention (%), specimen aged at 113° C.for 168 hours TSR 136° C. = Tensile strength retention (%), specimenaged at 136° C. for 168 hours Vol Res = Volume Resistivity (Ohm cm) @23° C. Wt Ret. = Retained weight (%) after 7 days @ 136° C.

Blends 7 and 8 both exhibit satisfactory properties before and afterheat aging. However, the purified ACW4 or SP-ACW4 (blend 8) results inlower hardness (i.e., increased plasticization efficiency) and lessloop-spew than the unpurified ACW4 (blend 7).

It is specifically intended that the present disclosure not be limitedto the embodiments and illustrations contained herein, but includemodified forms of those embodiments including portions of theembodiments and combinations of elements of different embodiments ascome within the scope of the following claims.

The invention claimed is:
 1. A single phase acetylated castor componenthaving less than about 0.2 wt % insoluble components after exposure to15° C. for at least one week, wherein the component has an iodine numberof less than 40 g I₂/100 g.
 2. The component of claim 1 wherein thesingle phase acetylated castor component is selected from the groupconsisting of a single phase acetylated castor oil, a single phaseacetylated castor wax, and combinations thereof.
 3. The component ofclaim 1 having a hydroxyl number from 0 to less than 5 as measured inaccordance with DIN
 53402. 4. The component of claim 1 having aviscosity less than 2000 mPa·s as measured in accordance with ASTM D 445at 25° C.
 5. The component of claim 1 having a turbidity from 1.0 NTU to50 NTU.
 6. The component of claim 1 having color less than 500 APHA. 7.A composition comprising: the single phase acetylated castor componentof claim 1; an epoxidized fatty acid ester; and the composition has lessthan 0.2 wt % insoluble components after exposure to 15° C. for at leastone week.
 8. The composition of claim 7 wherein the epoxidized fattyacid ester is selected from the group consisting of epoxidized soybeanoil, epoxidized propylene glycol dioleate, epoxidized palm oil,epoxidized linseed oil, epoxidized fatty acid methyl esters, epoxidizedderivatives of each of the foregoing, and combinations thereof.
 9. Apolymeric composition comprising: a polymeric resin; a plasticizercomposition comprising the single phase acetylated castor component ofclaim 1 and optionally an epoxidized fatty acid ester; and the polymericcomposition has a loop spew value from 0-2 as measured in accordancewith ASTM D
 3291. 10. The polymeric composition of claim 9 wherein theplasticizer composition comprises less than 0.2 wt % insolublecomponents after exposure to 15° C. for at least one week.
 11. Thepolymeric composition of claim 9 wherein the plasticizer compositioncomprises an epoxidized fatty acid ester selected from the groupconsisting of epoxidized soybean oil, epoxidized propylene glycoldioleate, epoxidized palm oil, epoxidized linseed oil, epoxidized fattyacid methyl esters, epoxidized derivatives of each of the foregoing, andcombinations thereof.
 12. A coated conductor comprising: a metalconductor; and a coating on the metal conductor, the coating comprisinga polymeric resin and a plasticizer composition comprising the singlephase acetylated castor component of claim 1 and optionally anepoxidized fatty acid ester.
 13. The coated conductor of claim 12wherein the plasticizer composition comprises less than 0.2 wt %insoluble components after exposure to 15° C. for at least one week. 14.The coated conductor of claim 12 wherein the plasticizer compositioncomprises an epoxidized fatty acid ester selected from the groupconsisting of epoxidized soybean oil, epoxidized propylene glycoldioleate, epoxidized palm oil, epoxidized linseed oil, epoxidized fattyacid methyl esters, epoxidized derivatives of each of the foregoing, andcombinations thereof.
 15. The component of claim 1 having an iodinenumber of less than or equal to 3 g I₂/100 g.